WO2009156050A1 - Composition elastomere auto-obturante - Google Patents

Composition elastomere auto-obturante Download PDF

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Publication number
WO2009156050A1
WO2009156050A1 PCT/EP2009/003949 EP2009003949W WO2009156050A1 WO 2009156050 A1 WO2009156050 A1 WO 2009156050A1 EP 2009003949 W EP2009003949 W EP 2009003949W WO 2009156050 A1 WO2009156050 A1 WO 2009156050A1
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WO
WIPO (PCT)
Prior art keywords
styrene
composition
phr
self
puncture
Prior art date
Application number
PCT/EP2009/003949
Other languages
English (en)
French (fr)
Inventor
Pierre Lesage
Vincent Abad
Original Assignee
Societe De Technologie Michelin
Michelin Recherche Et Technique S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe De Technologie Michelin, Michelin Recherche Et Technique S.A. filed Critical Societe De Technologie Michelin
Priority to JP2011513907A priority Critical patent/JP5615811B2/ja
Priority to US13/001,083 priority patent/US8871852B2/en
Priority to CN200980123640.9A priority patent/CN102066096B/zh
Priority to EP20090768899 priority patent/EP2303563B1/fr
Publication of WO2009156050A1 publication Critical patent/WO2009156050A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
    • B29C73/16—Auto-repairing or self-sealing arrangements or agents
    • B29C73/18—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression
    • B29C73/20—Auto-repairing or self-sealing arrangements or agents the article material itself being self-sealing, e.g. by compression the article material only consisting in part of a deformable sealing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/18—Layered products comprising a layer of natural or synthetic rubber comprising butyl or halobutyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0008—Compositions of the inner liner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C19/00—Tyre parts or constructions not otherwise provided for
    • B60C19/12—Puncture preventing arrangements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2030/00—Pneumatic or solid tyres or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2581/00—Seals; Sealing equipment; Gaskets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T152/00—Resilient tires and wheels
    • Y10T152/10—Tires, resilient
    • Y10T152/10495—Pneumatic tire or inner tube
    • Y10T152/10666—Automatic sealing of punctures [e.g., self-healing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers

Definitions

  • the present invention relates to self-sealing compositions and their use as anti-puncture layers in any type of "pneumatic" object, that is to say, by definition, any object that takes its usable form when inflated with air.
  • Self-sealing compositions capable of achieving such an objective, by definition capable of ensuring automatically, that is to say without any external intervention, the sealing of a tire in case of perforation of the latter by a foreign body such as a nail, are particularly difficult to develop.
  • a self-sealing layer In order to be usable, a self-sealing layer must satisfy many conditions of a physical and chemical nature. In particular, it must be effective over a very wide range of operating temperatures throughout the life of the tires. It must be able to close the hole when the piercing object remains in place; at the expulsion of the latter, it must be able to fill the hole and make the tire tight.
  • US-A-4.1 13,799 (or FR-A-2 318 042) has proposed as a self-sealing layer a composition comprising a combination of high and low butyl rubbers partially crosslinked molecular masses, possibly in the presence of a small part of thermoplastic styrene elastomer.
  • said composition comprises from 55 to 70% by weight of a tackifier.
  • US-A-4,228,839 has proposed as a self-sealing layer for a tire a rubber mixture containing a first polymeric material which degrades by irradiation, such as polyisobutylene, and a second polymeric material which crosslinks by irradiation, preferentially a butyl rubber.
  • US-A-4 426 468 has also proposed a self-sealing composition for a tire based on butyl rubber with very high molecular weight, crosslinked.
  • butyl rubbers exhibit significant hysteretic losses (high tan ⁇ level) over a broad temperature spectrum, a disadvantage that has repercussions on the self-sealing compositions themselves with a sharp increase in hysteresis. and a noticeable penalty for the rolling resistance of tires.
  • compositions based on butyl rubber may also have insufficient efficiency after the expulsion or delayed removal of a perforating object which has remained in place for a long time in the structure of the tire.
  • EP-B1-090 069 has in turn proposed self-sealing compositions devoid of butyl rubber, the specific formulation of which comprises per 100 parts by weight of a styrene-based thermoplastic elastomer, 80 to 140 parts by weight. a liquid plasticizer, 110 to 190 parts of a tackifying resin and 2 to 20 parts of an additive.
  • a large amount of tackifying resin in addition to the higher industrial cost it induces for the tires, can also penalize the rolling resistance of the tires because of a risk of excessive stiffening of the self-sealing composition.
  • the present invention relates to a self-sealing composition, usable especially as a puncture-resistant layer in a pneumatic object, comprising at least (pce meaning parts by weight per hundred parts of elastomers):
  • TPS thermoplastic styrene elastomer
  • the invention also relates to an airtight and puncture-resistant laminate which can be used in particular in a pneumatic object, comprising at least a first puncture-resistant layer comprising the self-sealing composition of the invention and a second airtight layer. .
  • the invention particularly relates to the use of such a self-sealing composition or such a laminate in a pneumatic object such as a tire, particularly when said composition or said laminate is disposed on the inner wall of said object or tire.
  • the present invention particularly relates to the use of the above-mentioned self-sealing composition or laminate in pneumatic tires intended for equipping tourism-type motor vehicles, SUVs ("Sport Utility Vehicles"), two wheels (in particular bicycles, motorcycles), aircraft, such as industrial vehicles selected from light trucks, "heavy goods vehicles” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery, other transport or handling vehicles.
  • SUVs Sport Utility Vehicles
  • two wheels in particular bicycles, motorcycles
  • aircraft such as industrial vehicles selected from light trucks, "heavy goods vehicles” - that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering machinery, other transport or handling vehicles.
  • the invention also relates per se to any pneumatic object, in particular a pneumatic tire, comprising a puncture-resistant layer or a laminate as described above.
  • any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term “from a to b” means the range from a to b (i.e., including the strict limits a and b).
  • composition or self-sealing material used in accordance with the invention is an elastomer composition
  • elastomer composition comprising at least one TPS elastomer saturated at a level of at least 30 phr (ie, 30 phr or more), an unsaturated TPS elastomer at a rate of at most 70 phr (ie, 70 phr or less), and more than 200 phr of oil as an extension oil of said TPS elastomers (pce means parts by weight per hundred parts of elastomers).
  • Styrenic thermoplastic elastomers are thermoplastic elastomers in the form of styrene-based block copolymers.
  • thermoplastic polymers and elastomers consist in a known manner of rigid polystyrene blocks connected by flexible elastomer blocks, for example polybutadiene, polyisoprene or poly (ethylene / butylene). They are often triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected. These TPS elastomers may also be diblock elastomers with a single rigid segment connected to a flexible segment.
  • each of these segments or blocks contains at least more than 5, usually more than 10 base units (e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer).
  • base units e.g., styrene units and isoprene units for a styrene / isoprene / styrene block copolymer.
  • At least 30 phr that is to say from 30 phr to less than 100 phr
  • at least 50 phr that is to say from 50 phr to less than 100 phr
  • a TPS elastomer saturated the latter being combined with: at most 70 phr (that is to say more than 0 phr to 70 phr), preferably at most 50 phr (that is to say more than 0 phr to 50 phr) of an unsaturated TPS elastomer .
  • the content of saturated TPS elastomer is within a range of at least 30 phr to less than 100 phr, and the level of unsaturated TPS elastomer (still present in the composition) is included in a range of from 0 pce to 70 pce maximum.
  • saturated TPS elastomer a TPS elastomer which contains no ethylenic unsaturation (i.e., no carbon-carbon double bond); unsaturated TPS elastomer, a TPS elastomer which is provided with ethylenic unsaturations, that is to say with carbon-carbon double bonds (conjugated or otherwise).
  • the saturated TPS elastomer is selected from the group consisting of styrene / ethylene / butylene (SEB), styrene / ethylene / propylene (SEP), styrene / ethylene / ethylene / propylene (SEEP), styrene / ethylene block copolymers butylene / styrene (SEBS), styrene / ethylene / propylene / styrene (SEPS), styrene / ethylene / ethylene / propylene / styrene (SEEPS) and mixtures of these copolymers.
  • SEB styrene / ethylene / butylene
  • SEP styrene / ethylene / propylene
  • SEEP styrene / ethylene block copolymers butylene / styrene (SEBS), styrene
  • said elastomer is selected from the group consisting of SEBS copolymers, SEPS copolymers and mixtures of these copolymers.
  • the unsaturated TPS elastomer is selected from the group consisting of styrene / butadiene (SB), styrene / isoprene (SI), styrene / butadiene / butylene (SBB), styrene / butadiene / isoprene (SBI) block copolymers, styrene / butadiene / styrene (SBS), styrene / butadiene / butylene / styrene (SBBS), styrene / isoprene / styrene (SIS), styrene / butadiene / isoprene / styrene (SBIS) and mixtures of these copolymers.
  • SB styrene / butadiene
  • SI styrene / isoprene
  • this unsaturated TPS elastomer is a triblock type copolymer selected from the group consisting of styrene / butadiene / styrene (SBS), styrene / butadiene / butylene / styrene (SBBS), styrene / isoprene / styrene (SIS) block copolymers.
  • SBS styrene / butadiene / styrene
  • SBBS styrene / butadiene / butylene / styrene
  • SIS styrene / isoprene / styrene
  • the presence of the unsaturated TPS elastomer in the self-sealing composition makes it possible to facilitate the adhesion of the latter to an at least partially unsaturated polymer matrix, for example a diene elastomer layer such as butyl rubber.
  • the level of saturated TPS elastomer be at least 60 phr, more preferably within a range of 70 to 95 phr, and that the level of unsaturated TPS elastomer is at most equal to 40 phr, preferably in a range of 5 to 30 phr.
  • the level of styrene in each TPS elastomer, saturated and unsaturated is between 5 and 50%. Below the minimum indicated, the thermoplastic nature of the elastomer may decrease significantly while above the maximum recommended, the elasticity of the composition may be affected. For these reasons, the styrene content is more preferably between 10 and 40%, in particular between 15 and 35%.
  • the Tg (measured by DSC (Differential Scanning Calorimetry) according to ASTM D3418, 1999) of the saturated TPS elastomer is less than -20 ° C, more preferably less than -40 ° C.
  • a value of Tg higher than these minima, implying a higher Tg of the composition itself, may reduce the performance of the self-sealing composition during use at a very low temperature; for such use, the Tg of the saturated TPS elastomer is more preferably still below -50 ° C.
  • the number-average molecular weight (denoted Mn) of each TPS elastomer, saturated and unsaturated is preferably between 50,000 and 500,000 g / mol, more preferably between 75,000 and 450,000.
  • Mn number-average molecular weight
  • the cohesion between the TPS elastomer chains, because of its dilution (amount of extender) may be affected; on the other hand, an increase in the temperature of use may affect the mechanical properties, including the properties at break, resulting in reduced performance "hot”.
  • a mass Mn that is too high can be detrimental to the flexibility of the composition, at the recommended oil extension rates.
  • a value in the range of 250,000 to 400,000 is particularly well suited, in particular to a use of the self-sealing composition in a tire.
  • the number-average molecular weight (Mn) of the TPS elastomers is determined in known manner by steric exclusion chromatography (SEC).
  • SEC steric exclusion chromatography
  • the sample is first solubilized in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
  • the equipment used is a chromatographic chain "WATERS alliance”.
  • the elution solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
  • a set of four WATERS columns in series, of trade names "STYRAGEL"("HMW7","HMW6E" and two "HT6E" is used.
  • the injected volume of the solution of the polymer sample is 100 ⁇ l.
  • the detector is a Differential refractometer "WATERS 2410" and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
  • the calculated average molar masses relate to a calibration curve made with polystyrene standards.
  • the two TPS elastomers previously described may constitute the whole of the elastomer matrix or the majority by weight (ie, for more than 50%, preferably more than 70%) of the latter when it comprises one or more other elastomers ( s), thermoplastic or not, for example of the diene type.
  • these two TPS elastomers are the only elastomers, and the only thermoplastic elastomers present in the self-sealing composition.
  • VTC TPE group VTC TPE group
  • Dryflex eg "Dryflex 967100”
  • Medium-Mediprene (eg” Mediprene 500 000M ")
  • Multibase eg” Multiflex G00 "
  • Unsaturated TPS elastomers such as, for example, SBS, SIS or SBBS, are also well known and commercially available, for example from Kraton under the name "Kraton D” (eg, products Dl 161, Dl 118, Dl 116, Dl 163 for examples of elastomers SIS and SBS), from Dynasol under the name “Calprene” (eg, products C405, C411, C412 for examples of SBS elastomers) or from Asahi under the name "Tuftec” (eg, product Pl 500 for an example SBBS elastomer).
  • Kraton D eg, products Dl 161, Dl 118, Dl 116, Dl 163 for examples of elastomers SIS and SBS
  • Dynasol eg, products C405, C411, C412 for examples of SBS elastomers
  • Tiftec eg, product Pl 500 for an example SBBS elastomer
  • TPS elastomers previously described, used in combination, have proved capable, after adding an extension oil at the recommended rate, of fulfilling the function of a high-performance self-sealing composition, as explained in detail later in the presentation.
  • the second essential constituent of the self-sealing composition is an extender oil (or plasticizing oil) used at a very high level, greater than 200 phr - more than 200 parts by weight per hundred parts of total elastomer (ie, saturated and unsaturated TPS elastomers, plus elastomer (s) complementary (s) where appropriate) - preferably greater than 250 phr.
  • extender oil or plasticizing oil
  • extension oil preferably of a slightly polar nature, capable of extending and plasticizing elastomers, especially thermoplastics, may be used.
  • these oils are liquids (that is to say, as a reminder, substances having the ability to eventually take the shape of their container), as opposed especially to resins that are inherently solid.
  • the extender oil is chosen from the group consisting of polyolefinic oils (that is to say derived from the polymerization of olefins, monoolefins or diolefins), paraffinic oils, naphthenic oils (low or high viscosity), aromatic oils, mineral oils, and mixtures of these oils.
  • the extender oil is selected from the group consisting of polybutenes, paraffinic oils and mixtures of these oils.
  • polyisobutylene oils are sold in particular by the company Univar under the name "Dynapak PoIy” (eg "Dynapak PoIy 190"), by BASF under the names “Glissopal” (eg “Glissopal 1000") or "Oppanol "(eg” Oppanol B 12 "); paraffinic oils are marketed for example by Exxon under the name “Telura 618" or by Repsol under the name "Extensol 51".
  • the number-average molecular mass (Mn) of the extender oil is preferably between 200 and 30,000 g / mol, more preferably between 300 and 10,000 g / mol.
  • Mn number-average molecular mass
  • the number average molecular weight (Mn) of the extender oil is determined by SEC, the sample being solubilized beforehand in tetrahydrofuran at a concentration of about 1 g / l; then the solution is filtered on a 0.45 ⁇ m porosity filter before injection.
  • the apparatus is the chromato graphic chain "WATERS alliance”.
  • the elution solvent is tetrahydrofuran, the flow rate is 1 ml / min, the temperature of the system is 35 ° C. and the analysis time is 30 minutes.
  • the injected volume of the solution of the polymer sample is 100 ⁇ l.
  • the detector is a differential refractometer "WATERS 2410" and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
  • the calculated average molar masses relate to a calibration curve made with polystyrene standards.
  • the extension oil content be between 200 and 900 phr, more preferably between 250 and 850 phr.
  • the self-sealing composition may be too rigid for some applications while beyond the maximum recommended, there is a risk of insufficient cohesion of the composition.
  • the level of extender oil is more preferably between 300 and 800 phr, in particular for use of the self-sealing composition in a tire.
  • additives may be added, typically in small amounts (preferably at levels of less than 20 phr, more preferably less than 10 phr), such as, for example, reinforcing fillers such as carbon black, non-reinforcing or inert fillers, lamellar fillers, protective agents such as anti-UV, anti-oxidants or antiozonants, various other stabilizers, coloring agents that can be advantageously used for coloring the self-sealing composition.
  • reinforcing fillers such as carbon black, non-reinforcing or inert fillers, lamellar fillers, protective agents such as anti-UV, anti-oxidants or antiozonants, various other stabilizers, coloring agents that can be advantageously used for coloring the self-sealing composition.
  • the self-sealing composition does not require the use of plasticizing or tackifying hydrocarbon resin
  • the invention also applies to cases where such a resin would be used.
  • the denomination "resin” is reserved, by definition, for a compound which is on the one hand solid at room temperature (23 ° C) (as opposed to a liquid plasticizer such as an oil), on the other hand compatible (c that is to say miscible with the rate used) with the elastomer composition for which it is intended, so as to act as a true diluent.
  • hydrocarbon resins By way of examples of such hydrocarbon resins, mention may be made of those selected from the group consisting of homopolymer or copolymer resins of cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated to DCPD), terpene homopolymer or copolymer resins. C5 homopolymer or copolymer resins, and mixtures of these resins.
  • CPD cyclopentadiene
  • DCPD dicyclopentadiene
  • the self-sealing composition could also comprise, still in a minority weight fraction relative to the TPS elastomers, polymers other than elastomers, such as, for example, thermoplastic polymers compatible with TPS elastomers.
  • composition or self-sealing material previously described is a solid (at 23 ° C) and elastic compound, which is characterized in particular, thanks to its specific formulation, by a very high flexibility and deformability.
  • pneumatic objects examples include pneumatic boats, balls or balls used for play or sport.
  • Such an anti-puncture layer is preferably disposed on the inner wall of the pneumatic object, covering it completely or at least in part, but it can also be completely integrated into its internal structure.
  • the thickness of the anti-puncture layer is preferably greater than 0.3 mm, more preferably between 0.5 mm and 10 mm (in particular between 1 and 5 mm). It will be readily understood that, depending on the specific fields of application, the dimensions and the pressures involved, the mode of implementation of the invention may vary, the puncture-resistant layer then having several preferential thickness ranges. Thus, for example, for tires of the tourism type, it may have a thickness of at least 0.5 mm, preferably between 1 and 5 mm. According to another example, for tire tires of heavy goods vehicles or agricultural vehicles, the preferred thickness may be between 1 and 6 mm. According to another example, for tires of vehicles in the field of civil engineering or for aircraft, the preferred thickness may be between 2 and 10 mm. Finally, according to another example, for bicycle tires, the preferential thickness may be between 0.4 and 2 mm.
  • the self-sealing composition described here has the advantage of not presenting, in a very wide range of tire operating temperatures, virtually no penalty in terms of rolling resistance compared to a tire having no such layer. self-sealing; compared to the usual self-sealing compositions, it very significantly improves the closing speed of the hole, in particular during the delayed withdrawal of a perforating object.
  • the usual self-sealing compositions have a high creepability. During the rolling of pneumatic tires, they are often driven from the sidewall of these bandages under the effect of centrifugal forces and accumulate under their top part. This is not the case for the compositions recommended by the present invention which can be arranged throughout the inner part of the tires.
  • the invention applies to cases where the self-sealing composition described above is used in a tire or other pneumatic object without necessarily being combined with an airtight layer.
  • the self-sealing composition is associated with at least one second airtight layer, to constitute a multi-layer laminate product, self-sealing and watertight.
  • air usable especially as internal wall of a pneumatic object such as a tire.
  • the second layer of the laminate may comprise any type of material capable of fulfilling the function of an airtight (or more generally gas) film, whether it be for example a metallic material or a polymer material .
  • this airtight layer has a thickness greater than 0.05 mm, more preferably between 0.05 and 6 mm (for example from 0.1 to 2 mm).
  • this second airtight layer comprises a butyl rubber composition.
  • butyl rubber should be understood in a known manner a copolymer of isobutylene and isoprene (abbreviated IIR), and the halogenated versions, preferably chlorinated or brominated, of this type of copolymer.
  • the butyl rubber is a halogenated butyl rubber or a halogenated and non-halogenated butyl blend.
  • Butyl rubber can be used alone or in combination with one or more other elastomer (s), especially diene elastomers (s) such as for example natural rubber or synthetic polyisoprene.
  • the airtight composition also comprises the various additives usually present in the airtight layers known to those skilled in the art, such as reinforcing fillers such as carbon black, lamellar fillers improving the seal (eg phyllosilicates such as kaolin, talc, mica, clays or clays modified (“organo clays”)), protective agents such as anti-oxidants or antiozonants, a crosslinking system (for example based on sulfur or peroxide), various processing agents or other stabilizers.
  • reinforcing fillers such as carbon black
  • lamellar fillers improving the seal eg phyllosilicates such as kaolin, talc, mica, clays or clays modified (“organo clays”)
  • protective agents such as anti-oxidants or antiozonants
  • a crosslinking system for example based on sulfur or peroxide
  • processing agents or other stabilizers for example based on sulfur or peroxide
  • the two layers of the above laminate can be assembled by any appropriate means, for example by a simple cooking operation, preferably under pressure (for example about ten minutes at 150 ° C. under 16 bars).
  • the self-sealing composition and the multilayer laminate described above are advantageously usable in tires of all types of vehicles, in particular in passenger car tires likely to run at very high speeds or tires for industrial vehicles such as heavy goods vehicles. likely to roll and operate under conditions of particularly high internal temperatures.
  • the single appended figure shows very schematically (without respecting a specific scale), a radial section of a tire according to the invention.
  • This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sidewalls 3 and two beads 4, each of these beads 4 being reinforced with a rod 5.
  • the crown 2 is surmounted by a tread represented in this schematic figure.
  • a carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9.
  • the carcass reinforcement 7 is in known manner constituted by at least one sheet reinforced by so-called "radial” cables, for example textile or metal, that is to say that these cables are arranged substantially parallel to each other and extend from one bead to the other so as to form an angle between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two beads 4 and passes through the middle of the crown reinforcement 6).
  • radial cables for example textile or metal
  • the tire 1 is characterized in that its inner wall comprises a multi-layer laminate (10) comprising at least two layers (10a, 10b), self-sealing thanks to its first layer (10a) and airtight thanks to at its second layer (10b).
  • a multi-layer laminate 10 comprising at least two layers (10a, 10b), self-sealing thanks to its first layer (10a) and airtight thanks to at its second layer (10b).
  • the two layers (10a, 10b) substantially cover the entire inner wall of the tire, extending from one flank to the other, at least up to the level of the tire hook. rim when the tire is in the mounted position.
  • the layer 10a could, however, cover only part of the airtight zone (layer 10b), for example only the crown area of the tire or extend at least from the top zone. to the shoulders or mid-flank (equator) of the bandage.
  • the laminate is arranged in such a way that the first self-sealing layer (10a) is radially outermost in the tire, with respect to the other layer (10b), as shown schematically on the attached figure.
  • the self-sealing layer (10a) covers the airtight layer (10b) on the side of the internal cavity 11 of the tire 1.
  • this layer (10a) ) is radially innermost, then disposed between the sealing layer (10b) and the remainder of the structure of the bandage 1.
  • the layer 10b (thickness 0.7 to 0.8 mm) is based on butyl rubber, has a conventional formulation for an "inner liner" which usually defines, in a bandage conventional pneumatic tire, the radially inner face of said tire for protecting the carcass reinforcement from the diffusion of air from the interior of the tire.
  • This layer 10b airtight thus allows the swelling and pressure maintenance of the bandage 1; its sealing properties enable it to guarantee a relatively low rate of pressure loss, making it possible to maintain the swollen bandage, in normal operating condition, for a sufficient duration, normally of several weeks or several months.
  • the layer 10a is constituted of a self-sealing composition comprising the three essential constituents that are a saturated elastomer SEBS ("G1654" of the company
  • the above self-sealing composition was prepared as follows.
  • the extruder used comprised two different feeds (hoppers) (SEBS on the one hand, SBS on the other hand) and a pressurized liquid injection pump for the polyisobutylene extension oil; it was provided with a die for extruding the product to the desired dimensions.
  • the layer 1 Oa disposed between the layer 10b and the cavity 1 1 of the tire, provides the tire effective protection against pressure losses due to accidental perforations, allowing the automatic closure of these perforations.
  • the composition serving as a self-sealing layer undergoes several constraints.
  • said composition creates a sealed contact zone all around the body.
  • the flexibility of the self-sealing composition allows it to interfere in openings of minimal size. This interaction between the self-sealing composition and the foreign body gives a seal to the area affected by the latter.
  • a perforation In case of accidental or voluntary removal of the foreign body, a perforation remains: it is likely to create a more or less important leak, depending on its size.
  • the self-sealing composition subjected to the effect of hydrostatic pressure, is sufficiently flexible and deformable to seal, by deforming, the perforation, preventing leakage of inflation gas.
  • the flexibility of the self-sealing composition makes it possible to easily withstand the forces of the surrounding walls, even during the phases of deformation of the loaded tire and while driving.
  • the tire provided with its puncture-resistant layer (10a) as described above can advantageously be produced before vulcanization (or firing).
  • the self-sealing composition is simply applied conventionally to the desired location for formation of the layer 10a.
  • the vulcanization is then carried out conventionally.
  • the TPS elastomers support the constraints related to the vulcanization step.
  • An advantageous manufacturing variant for those skilled in the tire industry, will for example consist in a first step of depositing the self-sealing composition flat on a manufacturing drum in the form of a layer. (“skim") of suitable thickness (for example 2 to 6 mm), before covering the latter with the airtight layer and then the rest of the tire structure, according to well-known manufacturing techniques of the invention. skilled person.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
PCT/EP2009/003949 2008-06-24 2009-06-03 Composition elastomere auto-obturante WO2009156050A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2011513907A JP5615811B2 (ja) 2008-06-24 2009-06-03 セルフシーリングエラストマー組成物
US13/001,083 US8871852B2 (en) 2008-06-24 2009-06-03 Self-sealing elastomer composition
CN200980123640.9A CN102066096B (zh) 2008-06-24 2009-06-03 自密封弹性体组合物
EP20090768899 EP2303563B1 (fr) 2008-06-24 2009-06-03 Composition elastomere auto-obturante

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FR0854154 2008-06-24
FR0854154A FR2932810B1 (fr) 2008-06-24 2008-06-24 Composition elastomere auto-obturante.

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JP (1) JP5615811B2 (ja)
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FR (1) FR2932810B1 (ja)
WO (1) WO2009156050A1 (ja)

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FR2955581A1 (fr) * 2010-01-28 2011-07-29 Michelin Soc Tech Procede de fabrication d'une composition d'elastomere a propriete auto-obturante
FR2955587A1 (fr) * 2010-01-28 2011-07-29 Michelin Soc Tech Composition d'elastomere pour objet pneumatique, a propriete auto-obturante
WO2013011111A1 (fr) * 2011-07-21 2013-01-24 Compagnie Generale Des Etablissements Michelin Bandage pneumatique pourvu d'une bande de roulement à base d'un élastomère thermoplastique
WO2013093608A1 (en) 2011-12-22 2013-06-27 Pirelli Tyre S.P.A. Self-sealing tyre for vehicle wheels
US9393837B2 (en) 2011-07-29 2016-07-19 Compagnie Generale Des Etablissements Michelin Self-sealing elastomer composition for a pneumatic object
US9403406B2 (en) 2012-09-17 2016-08-02 Compagnie Generale Des Etablissements Michelin Tire provided with a tread including a thermoplastic elastomer and carbon black
US9593266B2 (en) 2010-01-28 2017-03-14 Compagnie Generale Des Etablissements Michelin Method of manufacturing a self-sealing composition
US9849727B2 (en) 2011-05-12 2017-12-26 Compagnie Generale Des Etablissements Michelin Tire provided with a tread comprising a thermoplastic elastomer
FR3067357A1 (fr) * 2017-06-13 2018-12-14 Compagnie Generale Des Etablissements Michelin Compositions auto-obturantes

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FR3002491B1 (fr) * 2013-02-25 2015-03-27 Michelin & Cie Pneumatique auto-obturant comportant une armature de flanc supplementaire
FR3002490B1 (fr) * 2013-02-25 2015-03-27 Michelin & Cie Pneumatique auto-obturant comportant une armature de flanc supplementaire
US10086577B2 (en) 2015-12-01 2018-10-02 The Goodyear Tire & Rubber Company Method of making a self-sealing tire, and a tire
US20170165872A1 (en) 2015-12-11 2017-06-15 The Goodyear Tire & Rubber Company Modified tire sealant mixing device
WO2018156036A1 (en) 2017-02-23 2018-08-30 Aircom Automotive Sp. Z.O.O. Sp. K. A sealing composition for tires
CN109130710B (zh) * 2018-08-17 2021-01-01 安徽佳通乘用子午线轮胎有限公司 内附密封胶层具有防穿孔性能的充气轮胎及其制造方法
FR3086947B1 (fr) * 2018-10-03 2020-09-25 Michelin & Cie Compositions auto-obturantes
FR3103491B1 (fr) * 2019-11-27 2021-10-22 Michelin & Cie Composition auto-obturante pour objet pneumatique
CN112094473A (zh) * 2020-08-26 2020-12-18 中广核高新核材集团（东莞）祈富新材料有限公司 一种高韧可充气tpe材料及其制备方法
KR20220131734A (ko) 2021-03-22 2022-09-29 주식회사 크레펀 사용자의 소셜 콘텐츠를 활용한 거점 기반 미디어 디스플레이 장치용 콘텐츠 자동화 시스템 및 그 방법

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9677025B2 (en) 2010-01-28 2017-06-13 Compagnie Generale Des Etablissements Michelin Elastomer composition for a tire object having a self-sealing property
US8957132B2 (en) 2010-01-28 2015-02-17 Compagnie Generale Des Establissements Michelin Method for manufacturing an elastomeric composition having a self-sealing property
US9243133B2 (en) 2010-01-28 2016-01-26 Compagnie Generale Des Etablissements Michelin Elastomer composition for a tire object having a self-sealing property
WO2011092122A1 (fr) * 2010-01-28 2011-08-04 Societe De Technologie Michelin Composition d'elastomere pour objet pneumatique, a propriete auto-obturante
FR2955587A1 (fr) * 2010-01-28 2011-07-29 Michelin Soc Tech Composition d'elastomere pour objet pneumatique, a propriete auto-obturante
FR2955581A1 (fr) * 2010-01-28 2011-07-29 Michelin Soc Tech Procede de fabrication d'une composition d'elastomere a propriete auto-obturante
US9593266B2 (en) 2010-01-28 2017-03-14 Compagnie Generale Des Etablissements Michelin Method of manufacturing a self-sealing composition
WO2011092123A1 (fr) * 2010-01-28 2011-08-04 Societe De Technologie Michelin Procede de fabrication d'une composition d'elastomere a propriete auto-obturante
US9849727B2 (en) 2011-05-12 2017-12-26 Compagnie Generale Des Etablissements Michelin Tire provided with a tread comprising a thermoplastic elastomer
FR2978154A1 (fr) * 2011-07-21 2013-01-25 Michelin Soc Tech Bandage pneumatique pourvu d'une bande de roulement a base d'un elastomere thermoplastique
WO2013011111A1 (fr) * 2011-07-21 2013-01-24 Compagnie Generale Des Etablissements Michelin Bandage pneumatique pourvu d'une bande de roulement à base d'un élastomère thermoplastique
US9393837B2 (en) 2011-07-29 2016-07-19 Compagnie Generale Des Etablissements Michelin Self-sealing elastomer composition for a pneumatic object
WO2013093608A1 (en) 2011-12-22 2013-06-27 Pirelli Tyre S.P.A. Self-sealing tyre for vehicle wheels
US10300747B2 (en) 2011-12-22 2019-05-28 Pirelli Tyre S.P.A. Self-sealing tyre for vehicle wheels
US9403406B2 (en) 2012-09-17 2016-08-02 Compagnie Generale Des Etablissements Michelin Tire provided with a tread including a thermoplastic elastomer and carbon black
FR3067357A1 (fr) * 2017-06-13 2018-12-14 Compagnie Generale Des Etablissements Michelin Compositions auto-obturantes
WO2018229389A1 (fr) * 2017-06-13 2018-12-20 Compagnie Generale Des Etablissements Michelin Compositions auto-obturantes

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FR2932810A1 (fr) 2009-12-25
CN102066096A (zh) 2011-05-18
US20110165408A1 (en) 2011-07-07
JP2011525435A (ja) 2011-09-22
KR20110039279A (ko) 2011-04-15
JP5615811B2 (ja) 2014-10-29
EP2303563A1 (fr) 2011-04-06
KR101605924B1 (ko) 2016-03-23
US8871852B2 (en) 2014-10-28
FR2932810B1 (fr) 2010-08-20
EP2303563B1 (fr) 2012-10-10
CN102066096B (zh) 2016-06-08

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